CN106823469B - Super-hydrophobic super-oleophylic copper mesh and preparation method thereof without low-surface energy substance modification - Google Patents
Super-hydrophobic super-oleophylic copper mesh and preparation method thereof without low-surface energy substance modification Download PDFInfo
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- CN106823469B CN106823469B CN201710017156.4A CN201710017156A CN106823469B CN 106823469 B CN106823469 B CN 106823469B CN 201710017156 A CN201710017156 A CN 201710017156A CN 106823469 B CN106823469 B CN 106823469B
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- copper mesh
- oleophylic
- surface energy
- hydrophobic
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 52
- 239000010949 copper Substances 0.000 title claims abstract description 52
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000126 substance Substances 0.000 title claims abstract description 17
- 238000012986 modification Methods 0.000 title claims abstract description 13
- 230000004048 modification Effects 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000004070 electrodeposition Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 16
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims abstract description 9
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims abstract description 9
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims abstract description 9
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 229910001369 Brass Inorganic materials 0.000 claims description 8
- 239000010951 brass Substances 0.000 claims description 8
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 claims description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005530 etching Methods 0.000 abstract description 2
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- 239000011737 fluorine Substances 0.000 abstract description 2
- 239000007769 metal material Substances 0.000 abstract description 2
- 238000004381 surface treatment Methods 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 7
- 230000003068 static effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- LLJZKKVYXXDWTB-UHFFFAOYSA-N acetic acid;sodium Chemical compound [Na].[Na].CC(O)=O LLJZKKVYXXDWTB-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003653 coastal water Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
Landscapes
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The invention belongs to technical field of metal material surface treatment, disclose a kind of super-hydrophobic super-oleophylic copper mesh and preparation method thereof without low-surface energy substance modification.The preparation method is that: by copper mesh cleaning, drying, then the two poles of the earth of alternating current are done respectively with two panels copper mesh, containing thioacetamide, disodium ethylene diamine tetraacetate, Salzburg vitriol deionized water electroplate liquid in carry out electro-deposition, once purged high temperature drying at a temperature of 80~200 DEG C of copper mesh after the completion of electro-deposition, obtains the super-hydrophobic super-oleophylic copper mesh.The present invention can rapidly perform etching simultaneously at alternating current the two poles of the earth, be suitable for large area and produce, without using special equipment, treatment process is easily achieved；And the solution formula being related to is free of toxic fluorine-containing or carbon containing low-surface energy substance, and it is harmless to environment and human body, there is good economical and environmentally friendly benefit.
Description
Technical field
The invention belongs to technical field of metal material surface treatment, and in particular to it is a kind of without low-surface energy substance modification
Super-hydrophobic super-oleophylic copper mesh and preparation method thereof.
Background technique
With the rapid development of industry and marine petroleum exploitation, marine oil overflow Frequent Accidents.Marine draining accident will lead to
Substantial oil covers a piece of sea area, to cause far-reaching influence to environment；Meanwhile day common oily arbitrarily discharge also makes inland
Water oil stain dye in coastal waters is on the rise, and brings great harm to environment for human survival.How effectively to collect from water and clear
Except oils and organic pollutant have become world-class challenge, and attract wide public concern.Traditional deoiling method includes enclosing
Column oil suction method, biological oxidation process, controlled burning method and chemical dispersion method etc..But these methods due to it is at high cost, recycle
Rate is low and the unfavorable factors such as secondary pollution, constrains its practical application.
Since by the special infiltration sexual enlightenment in nature biotechnology surface, researcher just utilizes the special wellability of material
The research of water-oil separating is carried out to the different role of oil and water, and achieves a large amount of research achievement.For example, Chinese patent Shen
It please disclose in CN1387932A, CN101518695A and CN105268326A with super-hydrophobic and super oleophylic function grease
Separate nethike embrane.But these oil-water separation mesh films are all made of the low-surface energy substances system such as fluorochemical or carbon containing chain alkyl
It is standby, not only there is certain pollution to environment, but also its thermal stability is poor, easily decomposes cause ultra-hydrophobicity in use
Reduction.Though participating in Chinese patent application CN104801067A without low-surface energy substance, chemical reagent used is expensive and has
There is strong corrosive, higher cost is not easy large area preparation.
Summary of the invention
In order to solve the disadvantage that the above prior art and shortcoming, it is not necessarily to the primary purpose of the present invention is that providing one kind
The preparation method of the super-hydrophobic super-oleophylic copper mesh of low-surface energy substance modification.
Another object of the present invention is to provide a kind of super-hydrophobic super-oleophylic copper mesh being prepared by the above method.
The object of the invention is achieved through the following technical solutions:
A kind of preparation method of the super-hydrophobic super-oleophylic copper mesh without low-surface energy substance modification, including step is prepared as follows
It is rapid:
(1) by copper mesh cleaning, drying for standby；
(2) thioacetamide, disodium ethylene diamine tetraacetate and Salzburg vitriol are dissolved in deionized water, are electroplated
Liquid；
(3) it is heavy to carry out electricity in the electroplate liquid of step (2) for the two poles of the earth for making alternating current respectively with the two panels copper mesh of step (1)
Product；
(4) once purged high temperature drying at a temperature of 80~200 DEG C of copper mesh after the completion of electro-deposition, obtains described super-hydrophobic
Super oleophylic copper mesh.
Copper mesh of the present invention includes red copper net, brass screen and phosphor-copper net, and the aperture of copper mesh is 80~400 mesh.
Preferably, cleaning described in step (1) refers to successively with acetone, alcohol and deionized water ultrasonic cleaning.
Preferably, the concentration of thioacetamide is 0.02~0.2mol/L in electroplate liquid described in step (2)；Ethylenediamine tetraacetic
The concentration of acetic acid disodium is 0.1~0.5mol/L；The concentration of Salzburg vitriol is 0.02~0.1mol/L.
Preferably, the voltage of electro-deposition described in step (3) is 5~50V, and electrodeposition time is 5~60min.
Preferably, cleaning described in step (4) refers to successively with deionized water and washes of absolute alcohol.
Preferably, the time of step (4) described high temperature drying is 1~6h.
A kind of super-hydrophobic super-oleophylic copper mesh, is prepared by the above method.
Preparation method of the invention and obtained product have the following advantages that and the utility model has the advantages that
(1) present invention can rapidly perform etching simultaneously at alternating current the two poles of the earth, and electro-deposition processing technology is suitable for greatly
Area production, without using special equipment, treatment process is easily achieved；
(2) solution formula of the present invention is free of toxic fluorine-containing or carbon containing low-surface energy substance, to environment and the mankind
Body is harmless；
(3) the super-hydrophobic super-oleophylic copper mesh that the present invention obtains has certain thermal stability, significantly promotes this kind of material
Ability in practical applications.
Detailed description of the invention
Fig. 1 is the contact angle test result figure of embodiment 1 gained super-hydrophobic super-oleophylic red copper net and distilled water；
Fig. 2 is the contact angle test result figure of embodiment 1 gained super-hydrophobic super-oleophylic red copper net and diiodomethane；
Fig. 3 is the microscopic appearance figure of 2 gained super-hydrophobic super-oleophylic brass screen film layer of embodiment；
Fig. 4 is the underwater super oleophylic test result figure of 3 gained super-hydrophobic super-oleophylic phosphor-copper net of embodiment.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
Having a size of 50 × 30 180 mesh red copper nets, structure spy is obtained after electro-deposition and high temperature drying after surface preparation
Super-hydrophobic super-oleophylic surface outstanding is levied, following steps and process conditions are specifically included:
(1) copper sheet pre-processes: red copper net being cleaned by ultrasonic 5min with acetone, alcohol, deionized water respectively at room temperature, is blown
Blower drying, removes the greasy dirt and impurity on surface；
(2) electroplate liquid configures: by thioacetamide, disodium ethylene diamine tetraacetate and Salzburg vitriol are dissolved in deionized water
In, wherein the concentration of thioacetamide is 0.1mol/L, and the concentration of disodium ethylene diamine tetraacetate is 0.2mol/L, five hydrated sulfuric acids
The concentration of copper is 0.02mol/L；
(3) electro-deposition: using the copper mesh that two panels has pre-processed as the two poles of the earth of alternating current, 100ml step (2) is taken to prepare
Electroplate liquid under conditions of alternating voltage 40V, electro-deposition 15min；
(4) high temperature drying: the copper mesh after step (3) electro-deposition is taken out from electroplate liquid, with deionized water and anhydrous second
Alcohol dries up after rinsing, and the red copper net with super-hydrophobic super-oleophylic can be obtained after being subsequently placed at 150 DEG C dry 3h.
The red copper net of super-hydrophobic super-oleophylic obtained by the present embodiment is detected using optical contact angle measuring instrument, 6 μ L deionizations
Static contact angle of the water on this surface is 158.9 °, as shown in Figure 1；Static contact angle of the 6 μ L diiodomethanes on this surface be about
0 °, as shown in Fig. 2, i.e. surface has super-hydrophobicity and super-oleophilic.
Embodiment 2
Having a size of 50 × 30 120 mesh brass screens, structure spy is obtained after electro-deposition and high temperature drying after surface preparation
Super-hydrophobic super-oleophylic surface outstanding is levied, following steps and process conditions are specifically included:
(1) copper sheet pre-processes: brass screen being cleaned by ultrasonic 2min with acetone, alcohol, deionized water respectively at room temperature, is blown
Blower drying, removes the greasy dirt and impurity on surface；
(2) electroplate liquid configures: by thioacetamide, disodium ethylene diamine tetraacetate and Salzburg vitriol are dissolved in deionized water
In, wherein the concentration of thioacetamide is 0.05mol/L, and the concentration of disodium ethylene diamine tetraacetate is 0.4mol/L, five hydration sulphur
The concentration of sour copper is 0.08mol/L；
(3) electro-deposition: using the copper mesh that two panels has pre-processed as the two poles of the earth of alternating current, 100ml step (2) is taken to prepare
Electroplate liquid under conditions of alternating voltage 5V, electro-deposition 60min；
(4) high temperature drying: the copper mesh after step (3) electro-deposition is taken out from electroplate liquid, with deionized water and anhydrous second
Alcohol dries up after rinsing, and the brass screen with super-hydrophobic super-oleophylic can be obtained after being subsequently placed at 200 DEG C dry 1h.
The brass screen of super-hydrophobic super-oleophylic obtained by the present embodiment, the microscopic appearance of film layer using desk-top ESEM into
Row observation, as a result as shown in figure 3, as seen from Figure 3, brass screen Surface Creation a large amount of papillary protrusion, micro-nano are coarse
Structure feature is distinct.
Embodiment 3
Having a size of 50 × 30 300 mesh phosphor-copper nets, structure spy is obtained after electro-deposition and high temperature drying after surface preparation
Super-hydrophobic super-oleophylic surface outstanding is levied, following steps and process conditions are specifically included:
(1) copper sheet pre-processes: phosphor-copper net is cleaned by ultrasonic 10min with acetone, alcohol, deionized water respectively at room temperature,
Hair dryer drying, removes the greasy dirt and impurity on surface；
(2) electroplate liquid configures: by thioacetamide, disodium ethylene diamine tetraacetate and Salzburg vitriol are dissolved in deionized water
In, wherein the concentration of thioacetamide is 0.18mol/L, and the concentration of disodium ethylene diamine tetraacetate is 0.1mol/L, five hydration sulphur
The concentration of sour copper is 0.06mol/L；
(3) electro-deposition: using the copper mesh that two panels has pre-processed as the two poles of the earth of alternating current, 100ml step (2) is taken to prepare
Electroplate liquid under conditions of alternating voltage 30V, electro-deposition 5min；
(4) high temperature drying: the copper mesh after step (3) electro-deposition is taken out from electroplate liquid, with deionized water and anhydrous second
Alcohol dries up after rinsing, and the phosphor-copper net with super-hydrophobic super-oleophylic can be obtained after being subsequently placed at 80 DEG C dry 6h.
The phosphor-copper net of super-hydrophobic super-oleophylic obtained by the present embodiment is detected using optical contact angle measuring instrument, 6 μ L deionizations
Static contact angle of the water on this surface is 157.9 °, and static contact angle of the 6 μ L diiodomethanes on this surface is about 0 °, i.e., surface has
There are super-hydrophobicity and super-oleophilic, test results are shown in figure 4 for super oleophylic under water.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (7)
1. a kind of preparation method of the super-hydrophobic super-oleophylic copper mesh without low-surface energy substance modification, it is characterised in that including as follows
Preparation step:
(1) by copper mesh cleaning, drying for standby；
(2) thioacetamide, disodium ethylene diamine tetraacetate and Salzburg vitriol are dissolved in deionized water, obtain electroplate liquid；
(3) the two poles of the earth for making alternating current respectively with the two panels copper mesh of step (1), carry out electro-deposition in the electroplate liquid of step (2)；
(4) once purged high temperature drying at a temperature of 80~200 DEG C of copper mesh after the completion of electro-deposition, obtains the super-hydrophobic super parent
Oily copper mesh；
The copper mesh is selected from red copper net, brass screen or phosphor-copper net, and the aperture of copper mesh is 80~400 mesh.
2. a kind of preparation side of super-hydrophobic super-oleophylic copper mesh without low-surface energy substance modification according to claim 1
Method, it is characterised in that: cleaning described in step (1) refers to successively with acetone, alcohol and deionized water ultrasonic cleaning.
3. a kind of preparation side of super-hydrophobic super-oleophylic copper mesh without low-surface energy substance modification according to claim 1
Method, it is characterised in that: the concentration of thioacetamide is 0.02~0.2mol/L in step (2) described electroplate liquid；Ethylenediamine tetrem
The concentration of acid disodium is 0.1~0.5mol/L；The concentration of Salzburg vitriol is 0.02~0.1mol/L.
4. a kind of preparation side of super-hydrophobic super-oleophylic copper mesh without low-surface energy substance modification according to claim 1
Method, it is characterised in that: the voltage of step (3) described electro-deposition is 5~50V, and electrodeposition time is 5~60min.
5. a kind of preparation side of super-hydrophobic super-oleophylic copper mesh without low-surface energy substance modification according to claim 1
Method, it is characterised in that: cleaning described in step (4) refers to successively with deionized water and washes of absolute alcohol.
6. a kind of preparation side of super-hydrophobic super-oleophylic copper mesh without low-surface energy substance modification according to claim 1
Method, it is characterised in that: the time of step (4) described high temperature drying is 1~6h.
7. a kind of super-hydrophobic super-oleophylic copper mesh, it is characterised in that: be prepared by the described in any item methods of claim 1~6
It arrives.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710017156.4A CN106823469B (en) | 2017-01-10 | 2017-01-10 | Super-hydrophobic super-oleophylic copper mesh and preparation method thereof without low-surface energy substance modification |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710017156.4A CN106823469B (en) | 2017-01-10 | 2017-01-10 | Super-hydrophobic super-oleophylic copper mesh and preparation method thereof without low-surface energy substance modification |
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| Publication Number | Publication Date |
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| CN106823469A CN106823469A (en) | 2017-06-13 |
| CN106823469B true CN106823469B (en) | 2019-05-14 |
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| CN107313094B (en) * | 2017-06-15 | 2019-01-15 | 华南理工大学 | A kind of step electro-deposition prepares the methods and applications of close and distant conversion film layer |
| CN108857273B (en) * | 2018-06-13 | 2021-08-31 | 长春理工大学 | 7075 aluminum alloy super-hydrophobic surface preparation process |
| CN110075570B (en) * | 2019-05-05 | 2021-10-15 | 四川农业大学 | One-step method for preparing super-hydrophilic/underwater super-oleophobic oil-water separation mesh membrane and method |
| CN111218712B (en) * | 2020-01-09 | 2021-05-18 | 大连理工大学 | Preparation method of super-hydrophobic surface of electrolytic copper matrix |
| CN112206664B (en) * | 2020-10-22 | 2022-05-17 | 西北师范大学 | One-step anodic oxidation preparation process of inorganic flexible super-hydrophobic super-oleophylic copper mesh |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3095309A (en) * | 1960-05-03 | 1963-06-25 | Day Company | Electroless copper plating |
| CN101638777B (en) * | 2009-07-20 | 2011-01-12 | 北京工业大学 | Method for depositing copper sulphide nano film rapidly in low temperature |
| CN102228884B (en) * | 2011-06-20 | 2013-04-24 | 哈尔滨工业大学 | Preparation method and application of super-hydrophobic/super-lipophilic material in oil-water separation field |
| CN104524814A (en) * | 2015-01-17 | 2015-04-22 | 南昌航空大学 | Method for preparing super-hydrophobic super-oleophilic copper net without low-surface-energy preparation modification |
| CN105088297A (en) * | 2015-07-09 | 2015-11-25 | 吉林大学 | Preparation method of bionic oil-water separation copper net |
| CN105148562A (en) * | 2015-08-10 | 2015-12-16 | 中国海洋大学 | Candle-ash-assisted super-hydrophobic and super-oleophilic oil-water separation mesh film as well as preparation method and application of mesh film |
| CN105536296B (en) * | 2016-01-25 | 2019-01-29 | 华南理工大学 | Super-hydrophobic/super-oleophilic copper mesh and the preparation method and application thereof for water-oil separating |
| CN105797432A (en) * | 2016-03-25 | 2016-07-27 | 中山大学 | Preparation method of super-hydrophilic oil-water separating film |
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